JPH11147364A - Record sheet - Google Patents

Abstract

PROBLEM TO BE SOLVED: To have a superior print running property, ink absorptivity, an excellent image quality, water resistance and moisture resistance, in particular, be used preferably in a color ink jet printer recording sheet by permitting an ink receiving layer and/or its back surface to contain quaternary ammonium group-containing silicone resin particles. SOLUTION: The recording sheet is formed such that quaternary ammonium group-containing silicone resin particles are contained in a recording sheet formed by providing an ink receiving layer on one surface of a base material. For such a base material, each employed is paper, cloth, synthetic paper, a plastic film, a paper/plastic film, a cloth/plastic film, or the like. The quaternary ammonium group-containing silicone resin particles contains an RSiO3/2 unit (R is a univalent substituted or non-substituted hydrocarbon), or an RSiO3/2 unit and SiO2 group, and 1 mol.% of the group R in the molecular is a quaternary ammonium group-containing group. In addition, the receiving layer is blended with an ink absorptive resin.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a recording sheet used for an electrophotographic copying machine, an ink jet printer, a thermal transfer printer, and the like, and more particularly to a recording sheet having excellent print running properties in ink jet recording.

[0002]

2. Description of the Related Art With the spread of office automation in recent years, there has been an increasing demand for creating and recording documents in offices, and there has been a demand for a printer with low noise and excellent image quality. Electrophotographic copying machines, inkjet printers, and thermal transfer printers have been put to practical use to satisfy these requirements.
In recent years, color copying technology has reached the stage of completion, and color copiers / printers are gradually spreading. Above all, the spread of inkjet printers is remarkable. Ink jet printers use ink that is difficult to dry in order to prevent clogging of nozzles, and the components of this ink generally include a binder, a dye, a solvent, and additives dissolved in water. Therefore, it is necessary to use a recording sheet having good water absorbency, and special paper having good ink absorbency is usually used.

[0003]

Generally, paper is inferior in water resistance, moisture resistance and the like. Therefore, if a plastic film which does not have these disadvantages can be applied, the advantages can be utilized in various fields.

[0004] In the recording by an ink-jet printer, a plastic film-based one generally has poor slippage, poor print running properties, and is liable to cause troubles such as clogging inside the printer. An object of the present invention is to solve such a problem and to provide a recording sheet excellent in print running property.

[0005]

According to the present invention, there is provided a recording sheet comprising a base material having an ink receiving layer provided on one surface of a base material, wherein the ink receiving layer and / or the back surface are the fourth type. It is characterized by containing quaternary ammonium group-containing silicone resin particles.

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION Paper, cloth, synthetic paper,
Plastic films, paper / plastic films, cloth / plastic films, and the like are used. Among them, a plastic film is preferable from the viewpoint of water resistance and moisture resistance.
As the material of the plastic film, polyester,
Polyolefin, polyamide, polyester amide, polyether, polyimide, polyamide imide, polystyrene, polycarbonate, poly-ρ-phenylene sulfide, polyether ester, polyvinyl chloride, and poly (meth) acrylate are preferred. Further, these copolymers, blends, and further cross-linked ones can also be used. Further, among the above plastic films, polyesters such as polyethylene terephthalate, polyethylene 2,6-naphthalate, polyethylene α, β-bis (2-chlorophenoxy) ethane 4,4 ′
-Dicarboxylate, polybutylene terephthalate, etc. Among them, polyethylene terephthalate and polyethylene 2,6-naphthalate are preferable in consideration of mechanical properties, workability and other qualities, economy and the like.

The polyester in the present invention is a well-known polyester, specifically, for example, terephthalic acid, isophthalic acid, naphthalenedicarboxylic acid, bis-α, β (2-chlorophenoxy) ethane 4,4′-dicarboxylic acid, Obtained by polycondensing at least one kind of bifunctional carboxylic acid such as adipic acid and sebacic acid and at least one kind of glycol such as ethylene glycol, triethylene glycol, tetramethylene glycol, hexamethylene glycol, and decamethylene glycol. Polyester can be mentioned. In addition, the polyester may be blended or copolymerized with various kinds of polymers as long as the object of the present invention is not impaired, and may include an antioxidant, a heat stabilizer, a lubricant, a pigment, an ultraviolet absorber and the like. It may be. The intrinsic viscosity of the polyester (measured in orthochlorophenol at 25 ° C) is generally 0.4 to 2.0, preferably 0.5 to 2.0.
It is selected from the range of 1.0.

The polyester film used in the present invention comprises:
It is also possible to use those whitened by incorporating white inorganic particles into the polyester.

The white inorganic particles refer to inorganic particles which are almost non-colored, and include calcium carbonate, amorphous zeolite particles, anatase type titanium dioxide, calcium phosphate, calcium sulfate, barium sulfate, silica, alumina, kaolin,
Talc, clay and the like. In addition to such inorganic particles, fine particles precipitated by a reaction between a catalyst residue and a phosphorus compound in a polyester polymerization reaction system can also be used.

It is also possible to use a film in which fine bubbles are contained inside the film and whitened by scattering light with the bubbles. The formation of these fine bubbles is caused by the incompatibility of polymers such as poly-3-methylbutene-1, poly-4 in the film matrix, such as polyester.
-Methylpentene-1, polypropylene, polyvinyl-
Finely disperse t-butane, 1,4-trans-poly-2,3-dimethylbutadiene, cellulose triacetate, cellulose tripropionate, polychlorotrifluoroethylene, or the like, or add the above whitening fine particles and mix them. It is formed by stretching uniaxially or biaxially. Upon stretching, voids (bubbles) are formed around the immiscible polymer particles, which exhibit a light scattering action and are whitened. In addition, since it has fine bubbles, its specific gravity is low, and it also has cushioning properties, so that a clear image can be obtained.

When such a cell-containing polyester film is used, it is desirable that the apparent specific gravity of the cell-containing polyester film is 0.4 or more and 1.3 or less, preferably 0.6 or more and 1.2 or less. If the apparent specific gravity is lower than the above range, mechanical properties and thermal dimensional stability are inferior, which is not preferable.

When the polyester film has been subjected to a surface treatment, that is, a film subjected to a corona discharge treatment (in air, nitrogen, carbon dioxide gas, etc.) or an easy adhesion treatment, adhesion to the recording layer, water resistance, and water resistance are improved. It is more preferably used because its solvent properties and the like are improved. Various methods can be used for the easy adhesion treatment.Acrylic, urethane, polyester-based adhesives or the like applied in the film manufacturing process, or the film after uniaxial or biaxial stretching as described above. Those coated with various adhesives can be suitably used.

The base film may be a transparent film or a colored film.

The thickness of the substrate is not particularly limited, but is usually 10 μm or more and 500 μm or less, preferably 20 μm or more and 300 μm or less, and more preferably 30 μm or more and 250 μm or less.
It is desirable that it is not more than μm. When the base material is a paper / plastic film or a cloth / plastic film, it is preferable in terms of texture, and since the plastic film can be made thin, it is advantageous in terms of cost and is therefore preferable.

[0015] The present invention quaternary ammonium group-containing silicone resin particles in the, RSiO _3/2 units (wherein R is 1
Represents a substituted or unsubstituted hydrocarbon) or RS
and a iO _3/2 units and SiO ₂ units, one of the radicals R in the molecule
５０50 mol% is a quaternary ammonium group-containing group. If the amount of the quaternary ammonium group-containing group is less than 1 mol%, characteristics such as hydrophilicity and polarity cannot be obtained, which is not preferable. As the quaternary ammonium group-containing group, a general formula;

Embedded image (Wherein, R ¹ represents an alkyl group, Q ¹ represents an alkylene group having 3 to 6 carbon atoms, Q ² represents an alkylene group having 2 to 4 carbon atoms, and X ⁻ represents an anion). Is used. Further, those described in Japanese Patent Publication No. 2603291 can be effectively used. The particle size of the quaternary ammonium group-containing silicone resin particles is preferably from 0.01 to 50 μm, and more preferably from 0.1 to 30 μm. 4th
If the particle size of the quaternary ammonium group-containing silicone resin particles is smaller than 0.01 μm, the sliding effect is small, and the print running property is not improved. If the particle size of the quaternary ammonium group-containing silicone resin particles is larger than 50 μm, the image quality deteriorates, which is not preferable.

In the receiving layer of the present invention, an ink absorbing resin is mixed. As the ink absorbing resin, ethylene-vinyl acetate copolymer resin, ionomer resin, urethane resin,
Nylon resin, ethylene-acrylic acid copolymer resin, ethylene-ethyl acrylate copolymer resin, ethylene-methyl acrylate copolymer resin, ethylene-methacrylic acid copolymer resin, ethylene-vinyl alcohol copolymer resin, polyvinyl alcohol Examples include, but are not limited to, resins, polyvinyl butyral resins, polystyrene resins, polyalkylene oxide resins, gelatin, polyvinyl pyrrolidone, polyester resins, and cationic polymer resins.

The coating thickness of the receptor layer is not particularly limited,
It is 1 to 50 μm, preferably 2 to 30 μm. If the thickness is smaller than this, the ink absorbability of the obtained recording layer is inferior. If the thickness is larger than this, workability deteriorates and blocking tends to occur, which is not preferable.

In the present invention, when used as a recording sheet, it is preferable to impart an antistatic function from the viewpoint of adhesion of dust and the like due to static electricity and running properties. In order to impart antistatic properties, it is desirable to provide a receiving layer on one side of the substrate and provide an antistatic layer on the other side, or add an antistatic agent to the receiving layer.

The antistatic layer in the present invention includes a coating layer made of an antistatic agent, a resin layer containing an antistatic agent, and a vapor-deposited layer made of a metal or a metal oxide. Agent, conductive polymer, conductive carbon fine particles,
Examples include metal or metal oxide fine particles.

In the present invention, in order to further improve the running property and the heavy running property of the recording sheet, an antistatic agent is applied to the surface of the substrate opposite to the receiving layer, or a coating material containing inorganic or organic fine particles is used. It may be applied.

In the present invention, inorganic and / or organic particles may be dispersed in the receiving layer or the antistatic layer in order to further enhance the recording characteristics. Examples of the inorganic particles include silica, clay, talc, diatomaceous earth, calcium carbonate, barium sulfate, aluminum silicate, synthetic zeolite, alumina, zinc oxide, and mica. As the organic particles, for example, polymethyl methacrylate, polystyrene,
Plastic pigments such as copolymers thereof, polyvinyl chloride, polyethylene, polypropylene, polyvinylidene chloride, and polycarbonate can be preferably used, but are not limited thereto.

The receiving layer of the recording sheet according to the present invention comprises:
Various additives within a range that does not impair the characteristics of the present invention, such as silicone-based leveling agents, fluorine-based leveling agents, defoamers, thickeners, antistatic agents, antioxidants, ultraviolet inhibitors, fluorescent brightening agents Agents, dyes and the like.

The method of applying the recording layer is not particularly limited,
Gravure coating, reverse coating, kiss coating,
Methods such as a die coating method and a bar coating method can be used. At this time, not only the coatability is improved by applying a surface treatment such as a corona discharge treatment or a primer treatment in the air or other atmosphere as necessary before coating on the film, The receiving layer can be more firmly formed on the film. In addition, the coating agent concentration,
The conditions for drying the coating film are not particularly limited, but the drying conditions for the coating film are desirably performed within a range that does not adversely affect the properties of the substrate.

[0024]

DESCRIPTION OF THE PREFERRED EMBODIMENTS First, a method for evaluating various characteristics in the present invention will be described.

(1) Inkjet recording properties Epson inkjet printer PM700
Using C, a solid image and a photographic image were inkjet-recorded, and the image quality, ink absorbency, and print running property were evaluated, and the recordability was determined as follows. The image quality was evaluated by visual observation using a magnifying glass. The ink absorptivity was evaluated based on the degree of contamination of the recording layer with ink when the recording portion was rubbed once with a finger immediately after recording. Sheet 5
Zero sheets were continuously printed, and heavy running and sheet clogging were evaluated.

Image quality ：: very good (dots are uniform and clear) ：: good △: slightly poor ×: dot flow, repelling, bleeding, etc. Ink absorbency ：: very good (recording layer is completely dirty)な い: good △: slightly poor ×: ink is removed and the recording layer is stained Print runnability ：: no heavy running or sheet clogging at all △: heavy running or sheet clogging 1-2 sheets ×: (2) Water resistance of recorded image The recording sheet recorded by inkjet recording was immersed in water for 1 minute, and the degree of image flow was evaluated.

：: Image does not flow at all Δ: Image flows slightly ×: Image flows (3) Moisture resistance of recorded image Ink-jet recorded recording sheet is 40 ° C./80% R
The sample was allowed to stand in an atmosphere of H for one day, and the degree of image bleeding was evaluated.

○: The image does not blur at all △: The image blurs slightly ×: The image blurs (4) Specific gravity The film is cut into a 100 × 100 mm square, and the diameter is 10 m in a dial gauge (No. 2109-10, manufactured by Mitoyo Seisakusho).
The thickness of at least 10 points is measured with a probe attached with an m measuring element (No. 7002), and the average value d (μm) of the thickness is calculated. The film is weighed by a direct balance and the weight w (g) is read to the unit of 10 ^-4 g. At this time, the specific gravity was set to w / d × 100.

Next, the present invention will be described in detail with reference to Examples, but it should not be construed that the invention is limited thereto.

Example 1 A homopolymer chip of polyethylene terephthalate produced by a conventional method (intrinsic viscosity: 0.62, melting point: 25)
9 [deg.] C.) to obtain a biaxially stretched polyester film having a thickness of 100 [mu] m and a specific gravity of 1.4 by a conventional method. Corona discharge treatment was performed on the polyester film thus obtained. Next, a polyvinyl alcohol having a saponification degree of 35 mol% (LM-15, manufactured by Kuraray Co., Ltd.) and a cationic acrylic resin (Dulima-SPO-602, manufactured by Nippon Pure Chemical Co., Ltd.) were used as a receiving layer on the corona discharge treated surface. And a quaternary ammonium group-containing silicone resin particle (average particle diameter 5 μm) was dissolved in a water / methanol = 2/1 solvent so that the solid content ratio was 100/100/1, and the solid content was 30%.
% Of the solution, and applied with a reverse coater so that the thickness after drying becomes 15 μm, and dried at 120 ° C. for 1 minute to obtain a recording sheet of the present invention.

The recording characteristics of the recording sheet thus obtained were as shown in Table 1 below, and were excellent in recording performance, and excellent in print running property, water resistance and moisture resistance. Example 2 In Example 1, as a receiving layer, a polyester-urethane resin (NS120X manufactured by Takamatsu Yushi Co., Ltd.) and a cationic acrylic resin (Saftoma ST2 manufactured by Mitsubishi Chemical Corporation) were used.
100) and quaternary ammonium group-containing silicone resin particles (average particle size 0.5 μm) in a solid content ratio of 100/50.
The recording sheet of the present invention was obtained in the same manner as above except that the solvent was dissolved in a solvent of water / methanol = 2/1 so that the ratio became / 5, and the solution was applied as a solution having a solid content of 30%.

The recording properties of the recording sheet thus obtained were as shown in Table 1, and the recording sheet was excellent, and the printing runnability, water resistance and moisture resistance were also excellent. Example 3 Polyethylene Terephthalate Chip and Molecular Weight 40
The master chip to which the polyethylene glycol of No. 00 was added at the time of polymerization of polyethylene terephthalate was vacuum-dried at 180 ° C., and then mixed so as to be 89% by weight of polyethylene terephthalate, 1% by weight of polyethylene glycol, and 10% by weight of polymethylpentene. 300
Feed to extruder B heated to ° C. Further, after drying polyethylene terephthalate containing 10% by weight of calcium carbonate having an average particle diameter of 1.0 μm as described above,
Feed to extruder A. The polymers extruded from the extruders A and B were laminated so as to have a three-layer configuration of A / B / A, and formed into a sheet from a T die. Further, the unstretched film cooled and solidified by a cooling drum having a surface temperature of 25 ° C. was led to a group of rolls heated to 85 to 95 ° C., stretched 3.4 times in the longitudinal direction, and cooled by a group of rolls of 25 ° C.

Subsequently, the longitudinally stretched film was guided to a tenter while holding both ends of the film with clips, and stretched 3.6 times in a direction perpendicular to the longitudinal direction in an atmosphere heated to 130 ° C. Thereafter, heat fixing at 230 ° C. was performed in a tenter, and after uniform cooling, the film was cooled to room temperature and wound up to obtain a white film having a thickness of 100 μm and a specific gravity of 1.0. The laminated structure of the film was 5/90/5 μm. A recording sheet was obtained on the polyester film obtained by the above method as a receiving layer in the same manner as in Example 2.

The recording characteristics of the recording sheet thus obtained are as shown in Table 1. The recording sheet had good recording properties and excellent printing running property, water resistance and moisture resistance. Comparative Example 1 Example 1 , A recording sheet was obtained in the same manner except that the receiving layer did not contain quaternary ammonium group-containing silicone resin particles. The recording characteristics of the recording sheet thus obtained were as shown in Table 1 and were poor in print running property.

Table 1 below summarizes the above examples and comparative examples.

[0036]

[Table 1]

[0037]

As described above, the recording sheet of the present invention is a recording sheet having an ink receiving layer provided on one side of a base material, and a quaternary ammonium group on the ink receiving layer and / or the back side. Contains silicone resin particles for excellent print runnability, ink absorption, image quality,
It is excellent in water resistance and moisture resistance, and can be particularly preferably used as a recording sheet for a color inkjet printer.

Further, it can be preferably used in applications such as electrophotographic copying machines, fabric ink receivers, carbon ink receivers, heat-sensitive ink receivers including sublimation types, offset printing, and flexographic printing.

Claims (7)

[Claims] 1. A recording sheet comprising an ink receiving layer provided on one side of a substrate, wherein the ink receiving layer and / or the back side contain quaternary ammonium group-containing silicone resin particles. Recording sheet. 2. The recording sheet according to claim 1, wherein the substrate is a polyester film. 3. The recording sheet according to claim 1, wherein the substrate is a white polyester film. 4. The recording sheet according to claim 1, wherein the recording medium is a white polyester film having an apparent specific gravity of 0.4 to 1.3. 5. The recording sheet according to claim 1, wherein the base material is polyethylene 2,6-naphthalate. 6. The recording sheet according to claim 1, wherein the substrate is a paper / plastic film or a cloth / plastic film. 7. The recording sheet according to claim 1, wherein the recording sheet is for ink jet recording.